Reaction order approach and linear sweep voltammetry

3 Reaction order approach and linear sweep voltammetry 

The reaction order approach for the LSV response to simple reaction mechanisms, eqns. (49)—(51), has already been described. These equations are applied directly to experimental data and rate laws are derived before a mechanism or a theoretical model is considered. Since RA and RB are separable during LSV analysis, the changes in RB as a function of CA can be observed directly from djf p/d log v [72], When RB is changing with changes in CA, this slope will not be linear over large intervals but will appear to be linear over small intervals of v. For the reaction order analysis, CA was defined as the concentration when RB is half-way between the limiting values, usually 1 and 2, i.e. 1.5. In terms of n, multiples of CA, there are again three distinct cases which must be satisfied by f(n). They are n = 1 (,RB = 1.5), n 1 (RB = 1) and n 1 (RB = 2). These requirements are satisfied by eqn. (65) and illustrates how RB varies with n. 

For a complex mechanism where R B varies from 2 to 1, the corresponding equation is 

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